CN1467272A - Method for preparing cyanate ester water-based releasing agent for man-made board - Google Patents
Method for preparing cyanate ester water-based releasing agent for man-made board Download PDFInfo
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- CN1467272A CN1467272A CNA021408505A CN02140850A CN1467272A CN 1467272 A CN1467272 A CN 1467272A CN A021408505 A CNA021408505 A CN A021408505A CN 02140850 A CN02140850 A CN 02140850A CN 1467272 A CN1467272 A CN 1467272A
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Abstract
A process for preparing the water-type demoulding agent for isocyanate used to prepare artificial plate includes such steps as stirring while heating the emulsifier (nonylphenol polyoxyvinylether) for dissolving it, adding paraffin wax as isolating agent and dibutyltin dilaurate as catalyst, stirring, heating, holding the temp. adding preheated colloid as protecting agent and polyvinyl alcohol, and cooling. Its advantages are simple process, low cost, high productivity and demoulding effect, and long storage time.
Description
The invention belongs to a kind of fine chemistry industry preparation method.
At present, domestic wood-based plate is still blank with the research of isocyanic ester aqueous release agent, except that the minority review article, does not still have relevant research report or patent application.It is external because wood-based plate is relative with application early with the research of isocyanate adhesive, therefore existing isocyanic ester releasing agent product, but, have only patent, product introduction etc. because isocyanic ester ejection technique and the supporting use of isocyanate adhesive do not have disclosed research report.Low viscous hydrocarbon ils was mixed and made into emulsion with them and isocyanic ester during use, the isocyanate adhesive with interior release property that can make as the isocyanic ester releasing agent during for example English Patent 1176778 was used; Specially permit clear 59-43047,105096 in Japan and introduce to use paraffin to mix, prepare the isocyanic ester releasing agent with alkene class, silicone oil or liquid ester etc.In above-mentioned patent, they mainly isolate mechanism according to weak interface, use one to two kind of component to prepare isocyanic acid system releasing agent, and these releasing agents are evenly distributed at isocyanate adhesive, resin added can both satisfy service requirements when low generally speaking.When the applying glue inequality, gum spot, micelle, seep through occur, or resin added only relies on weak interface to isolate mechanism and is difficult to realize stripping result preferably when higher.And when using isocyanic ester to prepare shaving board,, be prone to gum spot, micelle because of the unequal reason of applying glue; And when preparing water-tolerant or waterproof level wood-based plate, often need higher resin added.Therefore the ejection technique of above-mentioned patent has been difficult to satisfy service requirements, need be according to new releasing agent Design Mechanism, and the ejection technique that the exploitation preparation is new and effective.
By polyisocynate monomer and polyvalent alcohol react under certain condition make and system in contain the product of the free isocyanato of a great deal of or, be referred to as the carbimide tackiness agent directly as the polyisocynate monomer of tackiness agent.Have a certain amount of free isocyanato and carbamate in the carbimide tackiness agent, because the difference of synthesis condition, raw material and condition of cure, also can contain certain imido grpup, carbonyl, ester group or their combination groups in the different isocyanate resin glue, as allophanate, replace urea, group that the biuret isopolarity is bigger.And has more active site on the metal platen surface in the wood-based plate manufacturing, under hot pressing condition, can have an effect with the bigger group of hydroxyl isopolarity in the carbimide tackiness agent, form second chemical bond, this is one of reason of isocyanate adhesive haftplatte
Free isocyanate groups then directly and the hydroxyl isoreactivity hydrogen generation chemical reaction of pressing plate, form first chemical bond, this is the major cause of isocyanic ester haftplatte, this haftplatte problem is the most serious, not only influence the surface quality of plate, and can pollute clamp surface, cleaning gets up to waste time and energy, and greatly reduces productivity.So the release problems of isocyanate resin glue is a problem that urgency is to be solved of isocyanate adhesive industrial applications.In conjunction with above-mentioned mechanism, how between carbimide tackiness agent that may contact and backing plate, to form one deck " partition wall " with backing plate, first and second chemical b `s that reduce or eliminate between carbimide and the backing plate are the keys that solve the demoulding, and forming the ideal interfacial failure between control backing plate and the shaving board is the main points of release method.
The objective of the invention is, invent a kind of new synthesis technique, utilize common feedstock production isocyanic ester aqueous release agent, make cost decreases, quality improves, and technology is simple.
Main design of the present invention is on the basis of isocyanic ester haftplatte mechanism, to have proposed new demoulding mechanism---the ternary mechanism of " sheltering+isolate+catalysis ", and use this mechanism design and the synthetic multiple new and effective water-based isocyanate demoulding
So-called free isocyanate groups design of sheltering haftplatte at forming strong first chemical bond with metal backing, can seal with the free isocyanate that backing plate reacts, make it to lose the ability that forms first chemical bond with metal backing, can prevent one of major reason of haftplatte effectively so this is such releasing agent; So-called isolation is that the multiple high polarity group of the haftplatte at forming second chemical bond with the active site on metal backing surface designs, can produce the high polarity group of the second chemical bond haftplatte with the metal backing active site and residual free isocyanate group that not masked dose is sheltered is isolated, further prevent the haftplatte of isocyanic ester, this is another major reason that such releasing agent can prevent haftplatte effectively; So-called catalysis is may have an effect with backing plate for fear of the residual free isocyanate group, in system, add the component that can play katalysis, accelerate the abundant effect of steel slab surface free isocyanate and its sequestering agent, make isocyanic ester being over, prevent the generation of its haftplatte comprehensively with basic consumption before backing plate contacts.
The prescription model of the isocyanic ester aqueous release agent that the present invention proposes is: in the system a certain proportion of sequestering agent, separant and promotor must be arranged.Be dispersed in aqueous phase, form comparatively stable emulsion or solution.
The water miscible liquid preparation of separant or promotor can obtain by following method: (1) has the emulsifying agent 1.8-2.8 part and the adding of water 62-80 part of metering in the reactor of agitator and thermometer, at room temperature stirred gently 10-15 minute, and avoided producing a large amount of bubbles; (2) then, in 20-30 minute, be warmed up to 70 ℃-75 ℃ gradually,, guarantee that emulsifying agent dissolves fully continuing stirring about 10 minutes under this temperature; (3) separant 65-70 part of adding thawing or preheating (also water insoluble as promotor, also add in the lump this moment) is continued stirring and is become pasty state up to system, needs 15-20 minute approximately; (4) continue to be warmed up to 90 ℃-95 ℃, accelerate stirring velocity, be incubated and stir about 20 minutes; (5) the colloid protective agent aqueous solution (65 ℃-70 ℃) that will measure again through preheating directly adds, and the temperature that adds the back system should not be lower than 70 ℃, and continues to stir 20 minutes.The consumption of noting water can not be higher than the moisture content that makes final releasing agent, and the concentration of emulsion water is preferably lower than the 15-25% of the moisture content of final releasing agent.(6) open water coolant, force 20 ℃-30 ℃ of cool to room temperature, discharging is stand-by.
The separant emulsion for preparing is taken out in right amount, and the water-soluble sequestering agent of adding metering, promotor, filler, water etc. stir up to they dissolvings, as accelerating dissolution rate, suitable elevated temperature, but should not be higher than 45 ℃, make the isocyanic ester aqueous release agent of requirement of the present invention thus.
The final preparation of releasing agent also can be carried out in the separant emulsion preparation later stage, generally be when cooling, when temperature is reduced to about 45 ℃, water miscible separant emulsion and water are added the dissolving stirring, but after they dissolve fully, continue to stir 10-20 minute, what make mixes fully, last cooling discharge.If the thermostability of water-soluble separant emulsion in the time of 70 ℃-85 ℃ is fine, also can be before adding for the second time water, promptly (4) in the separant emulsion preparation afterwards, (5) before.They are mixed with the solution preheating with the water that will add for the second time add, this moment system temperature about about 70 ℃-80 ℃, next again according to the step of separant emulsion preparation through behind insulation, stirring and the forced cooling, can the disposable releasing agent that makes.
The material of releasing agent sequestering agent mainly is among the present invention: the compound of hydroxyl, amino-contained or imido grpup compound or contain the compound of hydroxyl, amido, imido grpup simultaneously mainly contain: the small molecules unitary fatty alcohol, as ethanol, propyl alcohol, butanols etc.; Ethylene glycol, molecular weight are less than 1000 polyoxyethylene glycol and poly-Isopropanediol etc.; Ethylene glycol monoalkyl ether class, diglycol monotertiary alkyl ether are as their ether, propyl ether, butyl ether etc.; Glycerol, water-soluble urea-formaldehyde resin, water soluble phenol resin, urea, azanol, Monoethanolamine MEA BASF, diethanolamine, trolamine, TriMethylolPropane(TMP) etc.
Separant of the present invention has three classes---weak interface material type, film forming polymer substance and inorganic mineral powder.
The weak interface isolated substance mainly is paraffin and silicone oil, and is wherein effective with paraffin.Paraffin can be whiteruss or the bigger solid paraffin of molecular weight, also can directly use self-emulsifying paraffin wax or polyethylene wax etc., and it is the most convenient with whiteruss and self-emulsifying paraffin wax to discover in the use.Silicone oil mainly is to use methyl-silicone oil, and water-based silicone oil can use reluctantly.If use the separant of weak interface material as patent of the present invention, isolation agent can form the successive weak interface layer on the metal backing surface as long as satisfy, can prevent the isocyanic ester haftplatte effectively, general go up consumption account for non-volatile part of releasing agent 20～50% between, when more even, the surperficial content of isocyanate adhesive distribution is little, such as making shaving board with the way of spraying glue mixing, using aqueous macromolecule-isocyanate tackiness agent (API) to produce occasions such as glued board, the weak interface isolation agent can satisfy service requirements 20～35%; If consider can to occur after the glue system applying glue content of more gum spot, surperficial free isocyanate when higher, the weak interface isolation agent should suitably increase, and general consumption is at 30-60%.
This patent mainly uses following one-tenth mould polymer substance-polyvinyl alcohol, Walocel MT 20.000PV, resol, urea-formaldehyde resin, fluoro-resin, starch, flour, ground rice etc.Because the isolation mechanism of this class separant is to realize isolating by forming inert barriers,, generally account for releasing agent solid 5～70% so consumption is advisable with the film that can form adequate thickness.When high viscosity film forming matters such as independent use polyvinyl alcohol or Walocel MT 20.000PVs, or use fluoro-resin, consumption generally accounts for releasing agent solid 5～20%; When independent use urea-formaldehyde resin, resol, starch, flour, ground rice etc. were made filmogen, consumption generally accounted for solid 30～70%;
It is the same with the macromolecule filming substance mechanism to use inorganic mineral powder to make separant, all is that inertia is isolated, and mainly uses inorganic mineral powders such as wilkinite, high territory, fine particle lime carbonate, talcum powder, carbon black, silicon-dioxide, aluminum oxide.Consumption generally is a solid 30～90%.When being mixed with the use of solution shape, inorganic mineral powder after for some time is because be insoluble to or be insoluble in water, and therefore deposition generally is modulated into it use of paste or solid state gradually.
The employed promotor of isocyanic ester releasing agent comes down to the catalyzer of isocyanate reaction or the material that the reaction of isocyanic ester is had catalysis effectiveness, mainly be organic tin, tertiary amines, carboxylic metallic salt, and some can be used as the sequestering agent material again alkaline the time, as materials such as alkyl alkanolamine, carboxamides.Organic tin and tertiary amine catalyst are the most effective catalyzer of isocyanate resin reaction.This patent relates to concrete reaction promotor to be had: dibutyl tin dilaurate, two-2 ethyl hexanoic acid, two fourth tin, stannous octoate, stannous oleate, triethyl diamines, N, N-diethyl cyclohexylamine, N-alkyl morpholine, N, N, N ', N '-Tetramethyl Ethylene Diamine, tetramethyl butane diamine, 1,4 diaza-bicyclos (2,2,2)-octane, carboxamide, Monoethanolamine MEA BASF, diethanolamine, trolamine etc.Consumption is different and different because of catalyst type with usage, the organic tin catalyzer is 0.5～2% of releasing agent solid part, account for 0.1～0.5% of solution quality after the dilution,, must make emulsion earlier when therefore using because the organic tin compound is generally water insoluble; Tertiary amine catalyst and carboxylic metallic salt are because water-soluble and good catalytic activity, consumption generally accounts for releasing agent solid 1～5%, account for 0.1～1.0% of dilution back solution quality, can directly adding during use stirs in the release agent solution that modulates gets final product, and also can add in the releasing agent modulation process; Carboxamide, Monoethanolamine MEA BASF, diethanolamine, materials such as trolamine are the materials that the reaction of isocyanic ester is had catalysis effectiveness, though catalytic effect is not as organic tin catalyzer and tertiary amine catalyst, also can reach goodish catalysed promoted effect by improving its concentration, in addition because they all are the sequestering agents of this patent isocyanic ester releasing agent, so consumption generally accounts for releasing agent solid 15～40%, account for 2～5% of dilution back solution quality, can directly adding during use stirs in the release agent solution that modulates gets final product, and also can add in the releasing agent modulation process.
Other composition of isocyanic ester aqueous release agent mainly is to use paraffin and methyl-silicone oil to do that separant, organotin are done promotor, inorganic mineral powder is made separant, because they are water insoluble, by preparing more stable emulsion or suspension, make it to keep within a certain period of time dispersion system uniformly.All materials such as paraffin, methyl-silicone oil, organotin, inorganic mineral powder that can make are dispersed in the water, the tensio-active agent that its stability of while satisfies service requirements all can use, the for example ammonium oleate of sodium laurylsulfonate, new system, polyoxyethylene nonylphenol ether etc., even can directly use some commercially available emulsifying powder; Colloid protective agent mainly is polyvinyl alcohol solution and cellulose solution etc.
Advantage of the present invention: stripping result is good, and releasing agent reasonable in design is applicable to the isocyanic ester wood-based plate preparation of different resin addeds, pollution-free, do not influence the wood-based plate Joint strength, to the water ratio no requirement (NR) of wood-based plate, technology is simple, and production cost is low, the product long preservative period.
Embodiment:
With the isocyanic ester releasing agent among following feedstock production the present invention is example, and the blending process process of releasing agent is described.Raw material is formed and main effectiveness is respectively: paraffin is that separant, dibutyl tin dilaurate are that promotor, diethanolamine are that sequestering agent, polyvinyl alcohol are that colloid protective agent, polyoxyethylene nonylphenol ether are emulsifying agent.2.0 parts polyoxyethylene nonylphenol ethers and 80 parts of addings of water are had in the reactor of agitator and thermometer, at room temperature stirred gently 10 minutes, avoid producing a large amount of bubbles; Then, in 20-30 minute, be warmed up to 70 ℃-75 ℃ gradually,, guarantee that emulsifying agent dissolves fully continuing stirring about 10 minutes under this temperature; (3) add to melt or 2 parts of 70 parts in the paraffin of preheating and dibutyl tin dilaurates, continuing to stir becomes pasty state up to system, needs 15 minutes approximately; (4) continue to be warmed up to 90 ℃-95 ℃, accelerate stirring velocity, be incubated and stir about 20 minutes; (5) again 10 parts of diethanolamine, polyvinyl alcohol are dissolved in 80 parts of water for 3 parts, directly add after being preheating to 65 ℃, continue to stir 20 minutes.(6) open water coolant, force cool to room temperature (20 ℃-30 ℃), discharging, promptly make solid content and be 35% concentrated mold release agent, according to service condition the concentrated mold release agent solution with water being diluted to 4-10 during use doubly gets final product, this releasing agent outward appearance is a milky emulsion, and the pH value is between 8-10, and be not less than 3 months storage period.When being used to make the isocyanic ester shaving board, to resin added in 3-7%, even exist micelle and the gum spot also can the very desirable demoulding; Be used to prepare glued board, the core-board that isocyanic ester glueds joint, even the also demoulding ideally of obvious seep through is arranged.
Claims (5)
1, a kind of wood-based plate preparation method of isocyanic ester aqueous release agent; belong to the fine chemistry industry preparation method; it is characterized in that water miscible liquid, by stirring in reactor, heating, fully after the dissolving emulsifying agent; adding separant, the promotor continuation of melting stirs; heating, stirring, insulation again with sequestering agent, protectant aqueous solution, add after the preheating, stir; cool to room temperature then, discharging.
2, want the preparation method of 1 described wood-based plate according to right with the isocyanic ester aqueous release agent, it is characterized in that sequestering agent mainly comprises, the compound of hydroxyl, amino-contained, Asia, aminocompound, the compound that contains hydroxyl, amino, imido grpup simultaneously, that is, and the ethanol in the small molecules unitary fatty alcohol, propyl alcohol, butanols, ethylene glycol, molecular weight is less than 1000 polyoxyethylene glycol and poly-Isopropanediol; Ether, propyl ether, butyl ether in ethylene glycol monoalkyl ether class, the diglycol monotertiary alkyl ether; Water-soluble urea-formaldehyde resin, water soluble phenol resin, urea, azanol, Monoethanolamine MEA BASF, diethanolamine, TriMethylolPropane(TMP).
3, want the preparation method of 1 described wood-based plate according to right with the isocyanic ester aqueous release agent, it is characterized in that separant mainly comprises the weak interface material type, paraffin and silicone oil, the film forming polymer substance: polyvinyl alcohol, Walocel MT 20.000PV, resol urea-formaldehyde resin, fluoro-resin, starch, flour, ground rice, their solids component are 5-70%.
4, want the preparation method of 1 described wood-based plate according to right with the isocyanic ester aqueous release agent, it is characterized in that promotor mainly comprises dibutyl tin dilaurate, two-2 ethyl hexanoic acid, two fourth tin, stannous octoate, stannous oleate, triethyl diamines, N-alkyl morpholine, N, N, N, N-Tetramethyl Ethylene Diamine, tetramethyl butane diamine, 1,4 diaza-bicyclos (2,2,2)-octane, carboxamide, Monoethanolamine MEA BASF, diethanolamine, trolamine.
5; the wood-based plate according to claim 1 preparation method of isocyanic ester aqueous release agent; it is characterized in that 1.8 parts-2.8 parts of emulsifying agents and 62 parts of-80 parts of addings of water have in the reactor of agitator and thermometer; at room temperature stirred gently 10-15 minute; avoid producing a large amount of bubbles; then; in 20-30 minute, be warmed up to 70 ℃-75 ℃ gradually; under this temperature, continued to mix 10 minutes, and guaranteed that emulsifying agent dissolved fully, 65 parts-70 parts of the separants of adding thawing or preheating; continue stirring became the lake shape up to system in 15-20 minute; continue to be warmed up to 90 ℃-95 ℃, quicken to stir, be incubated and stir 20 minutes; again will be through the colloid protective agent water dissolution of preheating; directly add, the temperature that adds the back system should not be lower than 70 ℃, continues to stir 20 minutes; open water coolant, force the cool to room temperature discharging stand-by.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021408505A CN1326981C (en) | 2002-07-09 | 2002-07-09 | Method for preparing cyanate ester water-based releasing agent for man-made board |
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| CNB021408505A CN1326981C (en) | 2002-07-09 | 2002-07-09 | Method for preparing cyanate ester water-based releasing agent for man-made board |
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| CN1467272A true CN1467272A (en) | 2004-01-14 |
| CN1326981C CN1326981C (en) | 2007-07-18 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339200C (en) * | 2005-04-04 | 2007-09-26 | 上海康拜环保科技有限公司 | Demolding method for artificial MDI glue board |
| CN105033171A (en) * | 2015-07-27 | 2015-11-11 | 芜湖黄燕实业有限公司 | Release agent used for aluminum alloy hub die-casting die and preparation method thereof |
| CN105033172A (en) * | 2015-07-27 | 2015-11-11 | 芜湖黄燕实业有限公司 | Release agent used for aluminum alloy part die-casting die and preparation method thereof |
| CN105602467A (en) * | 2016-01-28 | 2016-05-25 | 江西绿丰新材料股份有限公司 | Release agent for isocyanate adhesive and preparing method of release agent |
| CN109576041A (en) * | 2018-11-29 | 2019-04-05 | 上海华谊精细化工有限公司 | A kind of environment-friendly type template paint and preparation method thereof |
| CN110640863A (en) * | 2019-09-30 | 2020-01-03 | 大亚人造板集团有限公司 | Organic silicon release agent for artificial board and preparation method thereof |
| US10787593B2 (en) | 2015-05-15 | 2020-09-29 | Wanhua Chemical Group Co., Ltd. | Emulsifiable isocyanate composition and preparation method and use thereof |
| CN114164063A (en) * | 2021-12-16 | 2022-03-11 | 万华化学集团股份有限公司 | Chemical cleaning agent for scaling substance of isocyanate heat exchanger, preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5658374A (en) * | 1995-02-28 | 1997-08-19 | Buckman Laboratories International, Inc. | Aqueous lecithin-based release aids and methods of using the same |
| CN1070224C (en) * | 1997-03-03 | 2001-08-29 | 王学环 | Multifunctional isolating agent and its producing method |
| JPH1171521A (en) * | 1997-06-23 | 1999-03-16 | Fuji Xerox Co Ltd | Lubricant-releasing material composition, lubricant-releasing material, production of lubricant-releasing membrane, lubricant-releasing membrane, member for fixation, fixing device, and color image formation |
-
2002
- 2002-07-09 CN CNB021408505A patent/CN1326981C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339200C (en) * | 2005-04-04 | 2007-09-26 | 上海康拜环保科技有限公司 | Demolding method for artificial MDI glue board |
| US10787593B2 (en) | 2015-05-15 | 2020-09-29 | Wanhua Chemical Group Co., Ltd. | Emulsifiable isocyanate composition and preparation method and use thereof |
| CN105033171A (en) * | 2015-07-27 | 2015-11-11 | 芜湖黄燕实业有限公司 | Release agent used for aluminum alloy hub die-casting die and preparation method thereof |
| CN105033172A (en) * | 2015-07-27 | 2015-11-11 | 芜湖黄燕实业有限公司 | Release agent used for aluminum alloy part die-casting die and preparation method thereof |
| CN105602467A (en) * | 2016-01-28 | 2016-05-25 | 江西绿丰新材料股份有限公司 | Release agent for isocyanate adhesive and preparing method of release agent |
| CN109576041A (en) * | 2018-11-29 | 2019-04-05 | 上海华谊精细化工有限公司 | A kind of environment-friendly type template paint and preparation method thereof |
| CN110640863A (en) * | 2019-09-30 | 2020-01-03 | 大亚人造板集团有限公司 | Organic silicon release agent for artificial board and preparation method thereof |
| CN114164063A (en) * | 2021-12-16 | 2022-03-11 | 万华化学集团股份有限公司 | Chemical cleaning agent for scaling substance of isocyanate heat exchanger, preparation method and application |
| CN114164063B (en) * | 2021-12-16 | 2023-08-11 | 万华化学集团股份有限公司 | Chemical cleaning agent for scaling substances of isocyanate heat exchanger, and preparation method and application thereof |
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| CN1326981C (en) | 2007-07-18 |
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